Mineral oil composition



Patented Jan. 9, 1945 MINERAL OIL COMPOSITION Orland M. Romwooabury, N.1., asslgnor to Socony-Vacunm Oil Company, Incorporated, New York, N.Y., a corporation of New York No Drawing. Application April 10, 1940,Serial No. 328,873

13 Claims.

This invention has to do in a general way with mineral oil compositionsand is more particularly related to mineral oil compositions of the typeused as lubricants, dielectrics, etc., to which an agent has been addedfor the purpose of improving the oil in certain respects. It is anobject of this invention to provide a novel class of mineral oiladdition' agents which will improve one or more important properties ofa mineral oil fraction. It is a further object to provide mineral oilcompositions containing such addition agents.

In my copending application Serial No. 222,755, filed August 3, 1938,now issued as Patent 2,197,- 835, of which this application is acontinuation in part, I have described ageneral class of metallo-wax-arycompounds asmineral oil addition agents which are multifunctional inthat they areelfective to reduce the pour point, improve the viscosityindex, and retard the deleterious effects of oxidation in the oil towhich they are added. The present invention is predicated upon thediscovery that the sulfur derivatives or, more specifically, thesulfides (monosulfides and polysulfides) of metalorganic compoundsof thetype disclosed in the aforesaid application are improved in certainrespects over the corresponding metalorganic compounds. sulfides myinvention also contemplates the corresponding derivatives of the relatedelements selenium and tellurium.

The present invention is concerned with sulfur, selenium or telluriumcondensation compounds corresponding to a particular class of themetalorganic compounds disclosed in the aforesaid application. Morespecifically, this invention is directed to the sulfides and relatedselenides and tellurides of alkyl substituted aryl metal oxides. Thealkylated aryl metal oxides corresponding to the sulfides and relatedcondensation products contemplated herein are disclosed in my copendingapplication Serial No. 206,683 filed May 7, 1938.

The addition agents of the present invention are, like those of the lastmentioned copending application, characterized by the presence of anhydroxyaromatic nucleus in which the hydroxyl hydrogen is substitutedwith its equivalent weight of metal. Also, like the addition agents of-the said copending application, the present addition agents arecharacterized by substitution of at least one nuclear hydrogen atomwithan oil solubilizing substituent, such as an alkyl group de- Inaddition ,to the densationproduct oil miscible. By the term oil miscibleor oil soluble I have reference to the property of remaining uniformlydispersed in mineral oil under normal conditions of handling and use.Preferably for obtaining an oil miscible condensation product ofmultifunctional properties this oil solubilizing alkyl group shouldcontain at least twenty carbon atoms.

. The oil addition agents of the present invention are distinguishedfrom those of copending application 206,683 in that they arecharacterized by the presence of at least two aromatic nuclei, having anOM substituent and an oil solubilizing substituent as aforesaid whichare interconnected by at least one atom of an element selected from thegroup consisting of sulfur, selenium, and tellurium. Throughintroduction of a sulfur linkage, for example, in the manner or mannersto be hereinafter described, I obtain what may be broadly termed asulfide of an alkyl-substituted aryl metal oxide in which the oxygen ofthe metal oxide group is attached to the aryl nucleus. This generalclass of sulfides of alkylated aryl metal,

oxides distinguishes over the corresponding general class of alkylatedaryl metal oxides in that the sulfides are of increased effectiveness inretarding the deleterious effects of oxidation in the 'oil. In thepreferred multifunctional class of compounds, wherein the aryl nucleusis substituted with heavy alkyl groups, I have found that thesesulfides, in general, possess increased pour rived from an aliphatichydrocarbon material of suflicient solubilizing value to render theconpoint depressing and viscosity index improving properties over thecorresponding multifunctional compounds in the alkylated aryl metaloxides. In addition to the last-mentioned improvements, themultifunctional sulfides also have improved inhibiting action againstthe formation of oxidation products. The improved inhibiting propertiesare particularly significant in retarding the development of acidity incertain types .of oils under certain conditions of use.

The compounds or condensation products contemplated herein as oiladdition agents may be characterized by the general formula in which Trepresents a monocyclic or polycyclic aromatic nucleus; 2, representssulfur, selenium, or tellurium; n represents a whole number from one tofour and R represents an alkyl group which should contain at least tencarbon atoms to impart mere oil solubility or miscibility to thecompound and should contain atleast twenty carbon atoms to impartmultifunctional properties to the compound. M represents at leaston'e'hydroxylgroup the hydrogen of which has bear substituted with itsequivalent weight of metal and Ya represents residual hydrogen or asubstituent group in the aryl nucleus '1, as will be hereinafter morefully described.

As. aforesaid, the preferred multifunctional oil improving agents arethose in which R of general formula I represents at least one heavyalkyl group having at least twenty carbon atoms, and, as willhereinafter appear, these so-called "heavy alkyl groups for impartingmultifunctional properties'to the compound may be derived from allphatichydrocarbon material predominantly comprised of aliphatic compounds ofat least twenty 7 or negative, or neutral oil-solubilizing effect.

Such residual hydrogen and substituents are, as

, aforesaid, indicated by Yb in the general formula,

wherein Y is defined as selected from the group consisting of hydrogen,hydroxyl, ester (organic or inorganic acyl group) keto, alkoxy, alkylsultions of the type contemplated herein are cobalt. tin, aluminum andsodium, with carbon atoms such as a petroleum wax or more i specialpreference given to tin. l

As aforesaid, the aryl nucleus T may be monocyclic or polycycliccorresponding, forexample, to phenol, hydroxydiphenyl, naphthoL-anthrolv and their derivatives. A preferred condensation product derivedfrom alkyl-substituted phenol (hydroxy benzene) may, in its simplestform, be

represented by the general formula. Ir 0M 0 Y r Y Since the condensationreaction employed in synthesizing the sulfides may be attended byfurther condensation beyond that indicated in Formula H, such furthercondensed compounds: hereinafter termed polymers" are contemplatedherein as coming within general Formula I and fide, aryl sulfide, aroxy,ether alcohol, aldehyde,

thioaldehyde, oxlme, amide, (organic or inorganic acyl group),thioamide, carbamide, aralkyl, aryl,

alkaryl, halogen, nitroso, amino, nitrosamine, amidine, imine, N-thio,diazo, hydrazine, cyano, azoxy, azo, and hydrazo radicals and 1)represents the number of Y substituents and is equal to zero or a wholenumber corresponding to the number of replaceable nuclear hydrogens notsubstituted with OM, 2n and R.

In general, it appears that any metal may be employed as the metal M incompounds or condensation products of the aforesaid type to providevaluable oiladdition agents. 'The metals contemplated herein may bebroadly classified as metals of groups I to VIII inclusive of theperiodic system. These metals comprise the following: the alkali metals:lithium, sodium, potassium, rubidium, and caesium; the alkaline earthgroup:

as coming under the terms sulfides, fcondensation products etc., asemployed herein. Poly-I mers of this character which may be associatedwith or formedinstead of the simple compo nd.

of Formula II may be represented by the follow- Also, where alkylationof the aryl nucleus has been effected to obtain a multifunctional product by a preferred procedure whichjinvolves the Friedel-Craftscondensation of a phenol with a halogenated high molecular weightaliphatic hydrocarbon material (such as chlorinated petroleum wax) suchcondensation may result in the formation of compounds or a mixture ofcomberyllium, magnesium, calcium, strontium, and

' are those now commercially available as the cerium and yttrium group:namely, a mixture of praseodymium, neodymium, samarium, europium,gadolinium, terbium, dypsprosium, holmium, erbium, thallium andlutecium.

The selection of a metal will, of course, depend to a certain extentupon the character of the oil to which the addition agent is added andthe conditions under which it is to be used. Certain metals such aslead, zinc and tin for example may contribute to the oilinesscharacteristics of the oil. A preferred group of metals which have beenincorporated in sulfidesof alkylated aryl metal oxides and tested inmineral oil composipounds in which two or more phenol groups areinterconnected by one or more aliphatic hydrocarbon chains.Alkylated'phenolsof this type when further reacted to form the sulfidesand. their phenate derivatives, may result in the formation of compoundsormixtures of compounds corresponding for example to the followinggeneral formulae: f

- rig-c c 9 5H 0 Olk OM V \R Y a a Y v H H. H H

H0---- 0 --0--.-- OH H I H In'the general Formulae IV and V above thehydrocarbon chains represent polyvalent alkyl groups corresponding .to Rof general Formula I above.

The foregoing discussion is not intended asia development of thespecific molecular composition or structure of the representativecompounds 7 2,868,878 7 or condensation products constituting themineral oil improving agents contemplated herein but is intended to bemerely indicative or illustrative of the possible compositionof additionagents coming within the general scope of this invention. These additionagents ,may be characterized as the sulfides (or corresponding selenidesand tellurides) of alkylated hydroxyaromatic as eicosylene, cerotene,melene, polymerized isocompounds in which the hydroxyl hydrogen issubstituted with its' equivalent weight of metal. Irrespective of anyfurther condensation toward "the formation of complex compounds of thetype illustrated in Formulae II to V inclusive, it will be observed thatin all cases the compounds or condensation products are characterized byhaving at least once, therein, the grouping corresponding to generalFormula I. These more complex condensation products are alsocharacterized by the fact thatthey contain at least two of the metal-oxyand alkyl substituted aryl nuclei interconnected by at least one atomfrom the group consisting of sulfur, selenium and tellurium.

As aforesaid the term sulflde," as used herein,

is inclusive of the monosulfides, disulfldes, trisulfldes,tetrasulfides, etc.; that is, it includes both monosulfides andpolysulfides and is also inclusive of such polymers and related .complexderivatives as maybe formed by the hereinafter described procedures.These sulfur derivatives or sulfides of alkylated aryl metal oxides arethe preferred class of addition agents contemplated herein and for thatreason the illustrative procedures and typical examples given hereinrelate to the sulfides. The corresponding selenides and tellurides are,however, contemplated by and come within the scope of the broadinventive concept.

The general procedure for synthesizing the sulj fides of alkylated arylmetal oxides is to first form the alkylated hydroxyaryl sulfide andthen'substitute the hydroxyl hydrogen with metal.

- The alkylated hydroxyaryl sulfides can be prepared by the reaction ofalkylated hydroxyaromatic compounds with sulfur or with sulfur halides.With sulfur dichloride for example the monosulfide linkage (11:1 ingeneral Formula I) is formed and with sulfur monochloride the disulfidelinkage (11:2) is formed. By reaction with elementary sulfur, the mainproducts contain monosulfide linkages with H2S evolved in thecondensation reaction. Sulfur condensation products or "sulfides ofhigher sulfur content can be formed by (a) reaction-of alkylatedthiophenols (aryl mercaptans) with sulfur monochloride or sulfurdichloride, and (b) reaction of a compound having a disulfl'cle linkagewith sulfur, or alkali polysulfldes or alkyl tetrasulflde.

The alkylation of the hydroxyaromatic compound may be carried out invarious ways. .A preferred procedure is to subject a hydroxyaromaticcompound or an oxyaromatic compound to a Friedel-Crafts condensationreaction with a halogenated aliphatic hydrocarbon, which for obtainingthe preferredmultifunctional addition agents should be an aliphatichydrocarbon containing at least twenty carbon atoms or a mixture ofaliphatic compounds predominantly comprised of compounds having at leasttwenty carbon atoms. This'alkylatlon may also be carried out withunsaturated hydrocarbons or aliphatic alcohols, using H2804 or anhydrousaluminum chloride as a catalyst. In alkylating phenols with hi hmolecular weight alcohols however, it is preferred to convert thealcohol to the corresponding halide (or polyhalide) and then condensethe alkyl halide butylene, etc., and myricyl alcohol, ceryl alcohol,etc.

The Friedel-Crafts synthesis is preferred for obtaining thealkylatedhydroxyaromatic compound, and as a source of the alkyl substituentpreference is given to mixed high molecular weight hydrocarbons typifiedby those which characterize the heavier products of petroleum, such asheavy petroleum oils of the lubricant type,

petrolatum and crystalline petroleum' wax or other compounds which willresult in relatively long chain aliphatic substituents. Specialpreference is given to petroleum wax (paraffin wax) ogomelting point notsubstantially less than about 1 F., which is predominantly comprised ofaliphatic hydrocarbo'nshaving a molecular weight of at least 350 andcontaining at least twenty carbon atoms. g

Hydroxyaromatic compounds which may be used in the alkylation reactionaremonoor polycyclic and monoor poly-hydric hydroxyaromatic compoundswhich may or may not be otherwise substituted, as hereinafter indicated.Specific examples of compounds which may be used in this reaction are:phenol, resorcinol, hydroquinone, catechol, cresol, xylenol,hydroxydiphenyl, benzylphenol, phenylethyl phenol, phenol resins,methylhydroxydiphenyl, alpha and beta naphthol, xylyl naphthol, 'benzylphenol, anthranohphenylmethyl naphthol, phenanthrol, anisole, betanaphthyl methyl ether, chlorphenol, and the like. Preference in generalis to the monohydroxy phenols otherwise unsubstituted, particularpreference being given to phenol and alpha and beta naphthol. Mixedalkyl-aryl and aralkyl-aryl ethers such as anisole andbeta-naphthylmethyl ether are given as examples because the Friedel-Crafts reactionwith these ethers is accompanied by some rearrangement,yielding free hydroxyl groups.

Where it is desired to obtain a compound or condensation product inwhich the aryl nucleus contains in addition to, or instead of, residualhydrogen.. a substituent of the type classified in general Formula I asYb, it is pointed out that with the exception of substituents such asaralkyl,

aryl, alkaryl, halogen, hydroxyl, and aroxy, such Y groups areintroduced after alkylating the hydroxyaromatic compound. The usualmethods -for the introduction of these substituents: into non-alkylatedhydroxyaromatic compounds may be employed in connection with thealkylated hydroxyaromatic compounds contemplated herein. To thoseskilled in the art, it will be apparent that the Y substituents aremainly derivatives of phenolic (-OH) groups, amino groups, aldehyde andketo groups and carboxyl groups. Methods for the introduction of suchbase substituents along with phenolic OM groups will be apparent frommethods described in 'my aforesaid copend ing application Serial No.222,755. It should also be pointed out that where nuclear substituents.are present containing methylene groups such as alkyl. keto,-ether,ester radicals, etc.. the same may also carry the Y type of substituentssuch as halogen, hydroxyl, amino, cyano, nitro, thio groups, etc.,excepting those which are of strictly aromatic origin, such as thoseresulting from di- -ent is derived from petroleum wax. The details in atypical procedure for synthesizing these socalled wax substitutedhydroxyaromatic compounds (wax phenol) are described in my copendingapplication 206,638. Briefly this procedure involves reacting achlorinated wax such as chlorinated parafiin wax with-a phenol in thepresence of a Friedel-Crafts catalyst at elevated temperature. Thechlorinated wax should have a chlorine content of from percent to 16percent and the reaction mixture may contain about three atomicproportions of chlorine (in a chlorwax of 16% chlorine content) to onemolecular proportion of phenol. A wax phenol obtained from such areaction mixture may be designated as wax phenol (3-46). Parentheticalexpressions of the type (A-B) will be used hereinafter in connectionwith the wax substituted derivatives to designate (A) the number ofatomic proportions of chlorine in the chlorinated wax reacted with onemol of hydroxyaromatic compound and (B) the chlorine content of thechlorinated wax. In the above example A=3 and B=16. The same designationwill also apply to the sulfides of the wax aryl metal oxides whichconstitute the ultimate product derived from the wax phenol.

Illustrative procedures which may be followed in preparing the sulfidesof alkyl substituted hydroxyaromatic compounds and the sulfides ofalkylated aryl metal oxides derived therefrom are given in the followingexamples, wherein the "alkylated phenol is preferably a wax substitutedphenol of the type last described above for obtaining a multifunctionaloil improving agent.

EXAMPLE ONE SYNTHESIS or ALKYLATED HYDROXYLARYL Summits A. Monosulfidelinkage Reaction mixture Reaction mixture Alkylated phenol mol 1 Sulfurmonochloride mol Carbon disulfide,. benzene, chlorbenzene or ethylenedichloride as solvent part by weight- 1 PROCEDURE The alkylated phenolis dissolved in the solvent and brought to a temperature of about 100F., followed by addition of the sulfur halide. The

.sulfur halide is introduced slowly, requiring about V hour for theaddition, followed by refluxing the mixture about one hour to completethe reaction. HCl is evolved in the reaction, resulting in fixation. ofsulfur in the aryl nucleus.

After completion of the condensation reaction,

the mixture is water-washed to remove the dissolved hydrochloric acid,followed by removal of diluents. to give the finished product.

C. Tri or tetrasulfide linkage By reaction of the disulfide type ofcompound with elementary sulfur or alkali polysulfides or alkyltetrasulfldes, one or two atoms of sulfur can be added to the disulfidelinkage, resulting in formation of the tri or tetrasulfide derivative,respectively. The use of alkyl tetrasulfides is preferred in this typeof reaction.

Reaction mixture Alkylated phenol "disulfider mol 1 Ethyl tetrasulfidemol 1 Carbon disulfide or ethylene dichloride as I solvent part byweight 1 Pnocrzmmn EXAMIPIE TWO METAL DERIVATIVES 0F ALKYLATEDHYDROXYARO- MA'IIC SULFIDES Th metal oxides (phenates, naphtholates,etc.) of alkylated aromatic sulfides may be obtained and purifiedaccording to the same general procedures described in my copendingapplication 206,683 for synthesizing alkylated aryl metal oxides.

In the' formation of the alkali metal derivative, the alkylated phenolsulfide is reacted with an alcoholate of the desired alkali metal. Inthe formation; of derivatives of other classes of metals, the preferredprocedure consists in treating the alkylated phenol sulfide with anequivalent of the salt of the desired metal in alcohol solution,followed by reaction with an'equivalent amount of a sodium alcoholate,resulting in the formation of the alcoholate of the desired metal as theinitial product. By heating the mixture to about 300 F. for a period ofabout one hour, the metal alcoholate is reacted with the hydroxyl groupresulting in the formation of the metal phenate derivative. Normalinorganic or fatty acid salts as well as the oxy salts thereof I can beused in the formation of the metal derivatives.

Typical compoundsor condensation products obtained according to theforegoing procedure where wax phenol (316), for example, was used as theinitial reactant may be designated as metal phenates of wax phenoldisulfide (3-46); metal phenates of wax-phenol monosulfides (3-16) etc.Where a wax substituted naphthol is used as the initial reactant theproducts may be similarly designated as metal naphtholates ofwax-naphthol sulfides.

To demonstrate the improved properties ob tained in mineral oil blendscontaining addition agents of the type contemplated herein, I haveconducted comparative tests with representative mineral oils alone andblended with typical sulfides of alkylated aryl metal oxides. Theresults of these tests are discussed in the following exainples.

EXAMPLE THREE Pom Pom Dnussron These tests were conducted with a motoroil having a Saybolt viscosity of 67 seconds at 210 F. and a pour pointof +20 F. The pour points of blends formed from this oil andrepresentative sulfides of wax-aryl metal oxides are given in Table Ibelow:

' Table I Addition agent None... Cogaltous phenete of wax-phenoldisulfide 1 staannous phenate ol wax-phenol disulflde l Aluminum phenateoi wax-phenol disulfide (3-16) commons" 51151518 'o'f vi blfdi 156132)sulfide (346) Stannous naphtholate of wax-alpha naphthol disulfide(3-15) EXANEPLE FOUR VISCOSITY INDEX IMPROVEMENT Table II Say. vis.Addition agent 3 2 100 F. 210 F. V. I

' Percent None 140. 7 41. 8 79. 3 Cobaltous phenate of wax phenoldisulflde (3-16) l 148. 4 42. 6 82. 6 (obaltous phenate of wax phenolmonosulflde (3-16) 1 149. 8 42. 82. 9 I Stannnus nephtholate of waxnephthol disulfide (345).... l 147. 1 42. 9 97. 6

EXAMPLE FIVE INHIBITION or OXIDATION In addition to the foregoing testswe have also made a test on an oil and an oil blend containing arepresentative improving agent of the type contemplated by thisinvention to determine the comparative behavior of the unblended oil andthe improved oil under actual operating conditions. The test was carriedout in a single cylinder CFR engine. The engine was operatedcontinuously over a time interval of 28 hours, with the cooling mediumheld at a temperature of about 390 F., at a speed 01. 1200 R. P. M.,which is equivalent to a road speed of about 25 miles per hour. The

blended oil, andoil B1. B: is ing aninhibitor.

B1=1% of the stannous phenate of wax disulflde (3-16) in mineral oil.

B2=1% of the stannous naphtholate of waxalpha naphthol disulfide (3-15)in mineral oil.

the same 011 containphenol Table III Percent slots filled Grams Oil-oarbon N. N.

' deposit 1 I 2 I s 4 5 a ,4 a

360 sec 360 360 see so so 60. 13.5 2.1 0 o o 0 o o o o 4.1 0.2 so 0 240360 360 70 so 40 18.3 2.3 o o o o- 0 o o o 6.4 0.7

The amount of addition agent used in the oil may be varied dependingupon the character of the oil with which it is blended, the conditionsunder which the oil is to be used and the properties desired in thefinal oil blend. These sulfides of alkylated aryl metal oxides may beusedin amounts ranging from 1 percent to 10 percent and, in general, oilcompositions of the desired improved properties may be obtained withamounts in the neighborhood of 1 percent.

It is to be understood that while I have described certain preferredprocedures which may be followed in synthesizing the sulfides ofalkylated aryl metal oxides of the typecontemplated herein and havereferred to various representative constituents thereof which renderthem preferred for use as oil addition agents, such prooil temperaturewas held at about F. during 7 cedures and examples are for illustrativepurposes only., The invention, therefore, is not to be considered aslimited to the specific examples given but includes within its scopesuch changes and modifications as fairly come within the spirit of theappended claims.

I claim:

1. An improved mineral oil composition comprising a mineral oil havingadmixed-therewith a minor proportion of an oil miscible condensationproduct of an alkyl substituted aryl metal oxide in which the oxygen ofthe metal oxide group is directly attached to the aryl nucleus and inwhich at least two alkyl substituted aryl nuclei are interconnected byat least one atom of an element selected from the group consisting ofsulfur, selenium and tellurium, the said alkyl substituents beingcomprised of aliphatic hydrocarbon groups containing at least 20 carbonatoms.

2. An improved mineral oil composition comprising a mineral oil havingadmixed therewith a'minor proportion of anoil miscible condensationproduct of a wax substituted aryl metal oxide in which the oxygen of themetal oxide group is directly attached to the aryl nucleus and in whichat least two wax substituted aryl nuclei are interconnected by at leastone atom of sulfur,

the said alkyl substituents being comprised of aliphatic hydrocarbongroups containing at least 20 carbon atoms. a 1

4. An improved mineral oil composition comprising a mineral oil havingadmixed therewith a minor proportion of an oil miscible condensa tionproduct of a Wax substituted aryl metal oxide in which the oxygen ofthe-metal oxide group is directly attached tothe aryl nucleus and areinterconnected by at least one atoni of sulfur;

5. An improved mineral oilcomposition comprising a mineral oil havingadmixed therewith a minor proportion of an oil miscible monosulfide ofan alkyl substituted aryl metal oxide in which the oxygen of the metaloxide group is directly attached to the aryl nucleus, the said aikylsub- 6. An improved mineral oil composition com prising a mineral oilhaving admixed-therewith a minor proportion of an oil miscible-polysulfide.

/ of an alkyl substituted aryl metal'oxidein which c in which at leasttwo wax substituted aryl nuclei in which the oxygen or the metal oxidegroup is directly attached to the aryl nucleus and in which at least twoaryl nuclei are interconnected by at least one atom of anelementselected from the group consisting of sulfur, selenium and telluriuni,the said alkyl substituents being comprised of aliphatic hydrocarbongroups containing at least 20 carbon atoms.

12. An improved mineral oil composition comprising a mineral oil" havingadmixed therewith a 'minor proportion of an oil miscible condensationproduct of -an alkyl substituted aryl metal oxide in which the oxygen ofthe metal oxide .stituentsbeing comprised of aliphatic hydrocarbongroups containing at least carbon atoms..

20: the said alkyl substituents, being comprised of the oxygen of themetal oxide group is directly attached to the aryl nucleus, the saidalkyl substituents being comprised of aliphatic hydrocarbon groupscontaining "at least 20 carbon atoms.

'7. An improved mineral oil composition com; prising a mineral oilhaving admixed therewith a minor proportion of an oil misciblemonosulflde of a wax substituted arylmetal oxide in which the oxygen ofthe metal oxide group is directly 7 attached to the aryl nucleus. v

8. An improved mineral oil composition comprisin a minor proportion ofan oil miscible polysulfide of a wax-substituted aryl metal-oxide inwhich the oxygen of the metal oxide group is directly,

attached to the aryl nucleus.

9. An improved mineral oil composition comprising a mineral oil havingadmixed therewith a minor proportion from about 1 percentto about 10percent of a metal phenate of a. wax substituted phenol sulfide. I i r10. An improved mineraloil composition comprisinga mineral oil havingadmixed therewith a minor proportion, from about percent to about 10percent, of a metal naphtholate of a wax substituted naphthol sulfide. 1

11. An improved mineral oil composition-comprising a mineral oil havingadmixed therewith a mineral oil having admixed therewith a minorproportion from about 1: percent to about 10 percent of the oil misciblecondensation product of an alkyl substituted aryl metal oxide groupisdirectly-attached'to the-aryl nucleus and in which at least two alkylsubstituted aryl nuclei are interconnected by at least one atom of anelement selected from the group consisting of sulfur, selenium andtellurium,the"metal.' in said metal oxide group being selected from thegroup consisting of cobalt, tin, aluminum and'sodium,

aliphatic hydrocarbon groups containing at least 20 carbon atoms. I

13. An improved mineral oil composition comprising a mineral oil havingadmixed therewith a minor proportion of a metalorganic condensationcompound characterized by having at least once therein the groupingcorresponding to the in which T represents an aromatic nucleus; Itrepresents at least one 'alkyl group containing at least twenty carbonatoms; Y is selected from the group consisting of hydrogen, hydroxyl,ester, keto, aikoxy, alkyl sulfide, aryl sulfide, aroxy,

ether alcohol, aldehyde, thioaldehyde, oxime,

amide, thioamide, carbamide, aralkyl, aryl, alkaryl, halogen, nitroso,ammo, nitrosamine, amidine, imine, N-thio, .diazo, hydrazine, cyano,azoxy, azo, and hydrazo radicals; b represents the number of Y's and isequal to zero or a whole number corresponding to replaceable hydrogenson the nucleus T not substituted with R, OM and Zn; M represents thehydrogen equivalent of a metal; 2 represents an element selected fromthe group consisting of sulfur, selenium and tellu-. rium; and nrepresents a whole number from one to four.

ORLAND M. RElFF.

